N′-(4-Hydroxy­benzyl­idene)benzohydrazide dimethyl­formamide solvate

Jing, Z.-L.; Fan, Z.; Yu, M.; Chen, X.; Deng, Q.-L.

doi:10.1107/S1600536805030679

N′-(4-Hydroxybenzylidene)benzohydrazide dimethylformamide solvate

Z.-L. Jing, Z. Fan, M. Yu, X. Chen and Q.-L. Deng

The components of the title solvate structure, C₁₄H₁₂N₂O₂·C₃H₇NO, are connected via N—H

O, O—H

N and O—H

O hydrogen bonds, leading to a chain motif.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030679/tk6258sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030679/tk6258Isup2.hkl Contains datablock I

CCDC reference: 287736

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.004 Å
R factor = 0.046
wR factor = 0.149
Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT411_ALERT_2_B Short Inter H...H Contact  H10    ..  H10     ..       2.05 Ang.

Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         46 Perc.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C9
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N3
PLAT331_ALERT_2_C Small Average Phenyl C-C Dist.   C9     -C14           1.37 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1     ..  N1      ..       2.64 Ang.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

One of the aims of investigating the structural chemistry of Schiff bases is to develop protein and enzyme mimics (Santos et al., 2001). As part of an investigation of the coordination properties of Schiff bases functioning as ligands, the present study details the molecular structure of the title compound, (I).

The asymmetric unit of (I) comprises one moelcule each of N'-(4-hydroxybenzylidene)benzohydrazide and dimethylformamide (Fig. 1). The key N1—N2, N1═C7 and C6—C7 bond lengths are 1.384 (3), 1.274 (3) and 1.465 (3) Å, respectively, which are consistent with those found in 2-hydroxy-3-methoxybenzaldehyde 2,4-dinitrophenylhydrazone (Jing et al., 2005). The non-H atoms of the phenol moiety are planar, with an r.m.s. deviation of 0.017 Å, and similarly the r.m.s. deviation of the N1/N2/C8–C14/O2 atoms from their least-squares plane is 0.073 Å. The dihedral angle between the aformentioned planes is 8.17 (10)°. Intermolecular N—H···O, O—H···N and O—H···O hydrogen bonds stabilize the crystal packing (Fig. 2). As detailed in Table 2, the H atom on O1 forms a strong interaction with atom O2ⁱ and these extend along the b axis to form a chain [symmetry code: (i) 2 − x, y − 1/2, 1/2 − z]. Additional stabilization to the chain are afforded by somewhat weaker O1—H···N2ⁱ interactions. In this sense, the hydroxyl H atom might be thought of as being bifurcated. The dimethylformamide molecules are connected to this chain via N—H···O3 interactions.

Experimental top

An anhydrous ethanol solution of 4-hydroxybenzaldehyde (1.22 g, 10 mmol) was added to an anhydrous ethanol solution of benzohydrazide (1.36 g, 10 mmol) and the mixture was stirred at 350 K for 5 h under nitrogen whereupon a yellow precipitate appeared. The product was isolated, recrystallized from ethanol and then dried in vacuo to give pure compound (I) in 87% yield (m.p. 504 K, literature 502 K (Kaupp et al., 2000). Bright-yellow single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of a dimethylformamide solution.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The structure of (I), with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A view of the crystal packing in (I); hydrogen-bonding interactions are shown as dashed lines.

N'-(4-Hydroxybenzylidene)benzohydrazide dimethylformamide solvate top

Crystal data top

C₁₄H₁₂N₂O₂·C₃H₇NO	F(000) = 1328
M_r = 313.35	D_x = 1.254 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2528 reflections
a = 15.518 (3) Å	θ = 2.7–22.5°
b = 9.3215 (18) Å	µ = 0.09 mm⁻¹
c = 22.942 (5) Å	T = 294 K
V = 3318.4 (11) Å³	Block, yellow
Z = 8	0.30 × 0.22 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3424 independent reflections
Radiation source: fine-focus sealed tube	1576 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.081
ϕ and ω scans	θ_max = 26.5°, θ_min = 1.8°
Absorption correction: multi-scan SADABS (Sheldrick, 1997a)	h = −19→14
T_min = 0.932, T_max = 0.983	k = −11→11
17730 measured reflections	l = −19→28

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.0552P)² + 0.9554P] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max < 0.001
3424 reflections	Δρ_max = 0.17 e Å⁻³
218 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0099 (9)

Crystal data top

C₁₄H₁₂N₂O₂·C₃H₇NO	V = 3318.4 (11) Å³
M_r = 313.35	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 15.518 (3) Å	µ = 0.09 mm⁻¹
b = 9.3215 (18) Å	T = 294 K
c = 22.942 (5) Å	0.30 × 0.22 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3424 independent reflections
Absorption correction: multi-scan SADABS (Sheldrick, 1997a)	1576 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.983	R_int = 0.081
17730 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.17 e Å⁻³
3424 reflections	Δρ_min = −0.15 e Å⁻³
218 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.93036 (13)	0.1580 (2)	0.14871 (8)	0.0628 (5)
H1	0.981 (2)	0.191 (4)	0.1334 (15)	0.125 (14)*
O2	0.94921 (12)	0.7889 (2)	0.41577 (8)	0.0792 (6)
N1	0.85740 (13)	0.6177 (2)	0.34808 (8)	0.0567 (6)
N2	0.81954 (15)	0.6977 (2)	0.39197 (9)	0.0566 (6)
H2	0.7577 (19)	0.684 (3)	0.3967 (11)	0.080 (9)*
C1	0.92519 (16)	0.4467 (3)	0.25591 (10)	0.0554 (7)
H1A	0.9616	0.5161	0.2715	0.066*
C2	0.95532 (16)	0.3550 (3)	0.21357 (10)	0.0556 (7)
H2A	1.0120	0.3629	0.2007	0.067*
C3	0.90214 (15)	0.2513 (3)	0.19000 (10)	0.0480 (6)
C4	0.81856 (15)	0.2404 (3)	0.20917 (11)	0.0563 (7)
H4	0.7824	0.1704	0.1938	0.068*
C5	0.78818 (16)	0.3330 (3)	0.25124 (11)	0.0576 (7)
H5	0.7312	0.3257	0.2635	0.069*
C6	0.84059 (15)	0.4364 (3)	0.27552 (10)	0.0481 (6)
C7	0.80812 (17)	0.5291 (3)	0.32214 (10)	0.0551 (7)
H7	0.7505	0.5231	0.3330	0.066*
C8	0.87134 (18)	0.7807 (3)	0.42500 (11)	0.0563 (7)
C9	0.83153 (16)	0.8596 (3)	0.47440 (10)	0.0520 (6)
C10	0.88213 (19)	0.9556 (3)	0.50354 (13)	0.0823 (10)
H10	0.9378	0.9727	0.4903	0.099*
C11	0.8527 (2)	1.0273 (4)	0.55183 (14)	0.0911 (10)
H11	0.8886	1.0916	0.5711	0.109*
C12	0.7716 (3)	1.0043 (4)	0.57135 (13)	0.0828 (10)
H12	0.7514	1.0528	0.6041	0.099*
C13	0.7197 (2)	0.9101 (4)	0.54295 (14)	0.0913 (11)
H13	0.6638	0.8946	0.5561	0.110*
C14	0.74972 (19)	0.8369 (3)	0.49435 (12)	0.0784 (9)
H14	0.7140	0.7720	0.4753	0.094*
O3	0.63555 (13)	0.6751 (2)	0.38773 (9)	0.0846 (7)
N3	0.50132 (14)	0.7690 (2)	0.38478 (10)	0.0687 (7)
C15	0.5643 (2)	0.6881 (3)	0.36595 (13)	0.0711 (8)
H15	0.5537	0.6349	0.3324	0.085*
C16	0.41875 (19)	0.7774 (4)	0.35486 (16)	0.0999 (11)
H16A	0.4187	0.7127	0.3223	0.150*
H16B	0.4096	0.8736	0.3412	0.150*
H16C	0.3734	0.7514	0.3813	0.150*
C17	0.5132 (2)	0.8582 (4)	0.43590 (14)	0.0992 (11)
H17A	0.5423	0.8041	0.4656	0.149*
H17B	0.4581	0.8889	0.4502	0.149*
H17C	0.5472	0.9405	0.4258	0.149*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0628 (13)	0.0704 (13)	0.0553 (11)	−0.0052 (10)	0.0097 (9)	−0.0136 (10)
O2	0.0582 (13)	0.1083 (17)	0.0711 (13)	−0.0117 (11)	0.0182 (10)	−0.0253 (12)
N1	0.0575 (14)	0.0679 (15)	0.0447 (11)	0.0064 (12)	0.0072 (10)	−0.0053 (11)
N2	0.0510 (14)	0.0701 (15)	0.0487 (12)	0.0028 (12)	0.0085 (11)	−0.0132 (11)
C1	0.0540 (17)	0.0634 (17)	0.0488 (14)	−0.0087 (13)	0.0039 (12)	−0.0046 (13)
C2	0.0499 (16)	0.0686 (18)	0.0482 (14)	−0.0065 (13)	0.0084 (12)	−0.0026 (14)
C3	0.0521 (16)	0.0546 (15)	0.0374 (12)	0.0003 (13)	0.0023 (11)	0.0028 (12)
C4	0.0491 (16)	0.0655 (18)	0.0542 (15)	−0.0095 (13)	0.0012 (12)	−0.0059 (14)
C5	0.0457 (15)	0.0729 (19)	0.0541 (15)	−0.0017 (14)	0.0075 (12)	0.0011 (15)
C6	0.0482 (15)	0.0553 (16)	0.0406 (13)	0.0042 (13)	0.0021 (11)	0.0037 (12)
C7	0.0516 (16)	0.0652 (18)	0.0485 (14)	0.0066 (14)	0.0060 (12)	0.0023 (14)
C8	0.0563 (18)	0.0669 (18)	0.0458 (14)	−0.0031 (15)	0.0088 (12)	0.0011 (13)
C9	0.0551 (16)	0.0566 (16)	0.0442 (13)	−0.0006 (13)	0.0086 (12)	0.0017 (13)
C10	0.074 (2)	0.093 (2)	0.080 (2)	−0.0127 (18)	0.0141 (17)	−0.0278 (19)
C11	0.096 (3)	0.088 (2)	0.089 (2)	−0.007 (2)	0.007 (2)	−0.034 (2)
C12	0.110 (3)	0.075 (2)	0.0640 (19)	0.011 (2)	0.0167 (19)	−0.0177 (17)
C13	0.078 (2)	0.118 (3)	0.078 (2)	−0.003 (2)	0.0313 (17)	−0.028 (2)
C14	0.071 (2)	0.098 (2)	0.0664 (18)	−0.0166 (17)	0.0194 (16)	−0.0242 (17)
O3	0.0567 (13)	0.1136 (18)	0.0835 (14)	0.0104 (12)	−0.0006 (11)	0.0066 (13)
N3	0.0550 (15)	0.0741 (16)	0.0769 (16)	0.0048 (13)	0.0096 (12)	0.0034 (14)
C15	0.063 (2)	0.079 (2)	0.0717 (19)	0.0011 (17)	0.0072 (16)	0.0040 (16)
C16	0.056 (2)	0.106 (3)	0.138 (3)	0.0074 (19)	−0.003 (2)	0.010 (2)
C17	0.107 (3)	0.103 (3)	0.088 (2)	0.012 (2)	0.018 (2)	−0.010 (2)

Geometric parameters (Å, º) top

O1—C3	1.358 (3)	C9—C14	1.366 (3)
O1—H1	0.91 (3)	C10—C11	1.372 (4)
O2—C8	1.229 (3)	C10—H10	0.9300
N1—C7	1.274 (3)	C11—C12	1.354 (4)
N1—N2	1.384 (3)	C11—H11	0.9300
N2—C8	1.348 (3)	C12—C13	1.357 (4)
N2—H2	0.97 (3)	C12—H12	0.9300
C1—C2	1.376 (3)	C13—C14	1.388 (4)
C1—C6	1.391 (3)	C13—H13	0.9300
C1—H1A	0.9300	C14—H14	0.9300
C2—C3	1.381 (3)	O3—C15	1.219 (3)
C2—H2A	0.9300	N3—C15	1.308 (3)
C3—C4	1.373 (3)	N3—C17	1.449 (4)
C4—C5	1.378 (3)	N3—C16	1.456 (4)
C4—H4	0.9300	C15—H15	0.9300
C5—C6	1.378 (3)	C16—H16A	0.9600
C5—H5	0.9300	C16—H16B	0.9600
C6—C7	1.465 (3)	C16—H16C	0.9600
C7—H7	0.9300	C17—H17A	0.9600
C8—C9	1.486 (3)	C17—H17B	0.9600
C9—C10	1.365 (4)	C17—H17C	0.9600

C3—O1—H1	109 (2)	C9—C10—H10	119.2
C7—N1—N2	115.8 (2)	C11—C10—H10	119.2
C8—N2—N1	117.7 (2)	C12—C11—C10	119.9 (3)
C8—N2—H2	127.0 (15)	C12—C11—H11	120.0
N1—N2—H2	115.3 (15)	C10—C11—H11	120.0
C2—C1—C6	120.4 (2)	C11—C12—C13	119.7 (3)
C2—C1—H1A	119.8	C11—C12—H12	120.2
C6—C1—H1A	119.8	C13—C12—H12	120.2
C1—C2—C3	120.6 (2)	C12—C13—C14	120.3 (3)
C1—C2—H2A	119.7	C12—C13—H13	119.8
C3—C2—H2A	119.7	C14—C13—H13	119.8
O1—C3—C4	118.7 (2)	C9—C14—C13	120.3 (3)
O1—C3—C2	121.9 (2)	C9—C14—H14	119.9
C4—C3—C2	119.4 (2)	C13—C14—H14	119.9
C3—C4—C5	120.0 (2)	C15—N3—C17	120.2 (3)
C3—C4—H4	120.0	C15—N3—C16	122.2 (3)
C5—C4—H4	120.0	C17—N3—C16	117.6 (3)
C6—C5—C4	121.3 (2)	O3—C15—N3	126.8 (3)
C6—C5—H5	119.4	O3—C15—H15	116.6
C4—C5—H5	119.4	N3—C15—H15	116.6
C5—C6—C1	118.3 (2)	N3—C16—H16A	109.5
C5—C6—C7	120.3 (2)	N3—C16—H16B	109.5
C1—C6—C7	121.3 (2)	H16A—C16—H16B	109.5
N1—C7—C6	121.2 (2)	N3—C16—H16C	109.5
N1—C7—H7	119.4	H16A—C16—H16C	109.5
C6—C7—H7	119.4	H16B—C16—H16C	109.5
O2—C8—N2	121.7 (2)	N3—C17—H17A	109.5
O2—C8—C9	120.6 (2)	N3—C17—H17B	109.5
N2—C8—C9	117.7 (2)	H17A—C17—H17B	109.5
C10—C9—C14	118.2 (2)	N3—C17—H17C	109.4
C10—C9—C8	117.3 (2)	H17A—C17—H17C	109.5
C14—C9—C8	124.4 (2)	H17B—C17—H17C	109.5
C9—C10—C11	121.6 (3)

C7—N1—N2—C8	172.5 (2)	N1—N2—C8—C9	−176.3 (2)
C6—C1—C2—C3	−0.1 (4)	O2—C8—C9—C10	8.8 (4)
C1—C2—C3—O1	−179.1 (2)	N2—C8—C9—C10	−172.8 (2)
C1—C2—C3—C4	0.0 (4)	O2—C8—C9—C14	−167.5 (3)
O1—C3—C4—C5	179.7 (2)	N2—C8—C9—C14	10.9 (4)
C2—C3—C4—C5	0.5 (4)	C14—C9—C10—C11	0.4 (5)
C3—C4—C5—C6	−1.0 (4)	C8—C9—C10—C11	−176.1 (3)
C4—C5—C6—C1	0.9 (4)	C9—C10—C11—C12	−0.5 (5)
C4—C5—C6—C7	−177.0 (2)	C10—C11—C12—C13	0.1 (5)
C2—C1—C6—C5	−0.4 (4)	C11—C12—C13—C14	0.4 (5)
C2—C1—C6—C7	177.6 (2)	C10—C9—C14—C13	0.1 (4)
N2—N1—C7—C6	−179.0 (2)	C8—C9—C14—C13	176.3 (3)
C5—C6—C7—N1	174.7 (2)	C12—C13—C14—C9	−0.5 (5)
C1—C6—C7—N1	−3.2 (4)	C17—N3—C15—O3	1.6 (5)
N1—N2—C8—O2	2.0 (4)	C16—N3—C15—O3	179.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.91 (3)	2.64 (4)	3.316 (3)	132 (3)
O1—H1···O2ⁱ	0.91 (3)	1.81 (4)	2.677 (3)	158 (3)
N2—H2···O3	0.97 (3)	1.91 (3)	2.864 (3)	166 (2)

Symmetry code: (i) −x+2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₂O₂·C₃H₇NO
M_r	313.35
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	294
a, b, c (Å)	15.518 (3), 9.3215 (18), 22.942 (5)
V (Å³)	3318.4 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan SADABS (Sheldrick, 1997a)
T_min, T_max	0.932, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	17730, 3424, 1576
R_int	0.081
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.149, 0.98
No. of reflections	3424
No. of parameters	218
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15

Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997b), SHELXTL (Bruker, 1999), SHELXTL.